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| United States Patent |
5,773,538
|
|
Feiring
|
June 30, 1998
|
Process for polymerization of olefinic monomers
Abstract
Free radically polymerizable olefinic monomers may be polymerized by using
a fluorinated alkyl sulfonyl chloride or bromide and optionally a lower
valent metal compound as an initiator system. Monomers such as styrenes,
(meth)acrylics, halogenated olefins and vinyl ethers may be polymerized to
a variety of thermoplastics or elastomers.
| Inventors:
|
Feiring; Andrew Edward (Wilmington, DE)
|
| Assignee:
|
E. I. du Pont de Nemours and Company (Wilmington, DE)
|
| Appl. No.:
|
895598 |
| Filed:
|
July 16, 1997 |
| Current U.S. Class: |
526/146; 526/254; 526/329.7; 526/346 |
| Intern'l Class: |
C08F 004/06 |
| Field of Search: |
526/146,94,346,329.7,254
|
References Cited
U.S. Patent Documents
| 2776952 | Jan., 1957 | Bredereck et al. | 526/146.
|
Other References
M. Asscher et al, J. Chem. Soc. (1964) pp. 4962-4971.
A. Orochov et al, J. Chem. Soc. (1969), pp. 255-259.
N. Kamigata et al, J. Chem. Soc., Perkin Trans. I (1991) pp. 627-633.
V. Percec et al, Macromolecules, vol. 28, pp. 7970-7972 (1995) and vol. 29,
pp. 3665-3668 (1996).
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Sarofim; N.
Claims
What is claimed is:
1. A polymerization process, comprising, contacting, at a temperature of
about 50.degree. C. to about 150.degree. C., a free radically
polymerizable olefin with a fluorinated alkyl sulfonyl chloride or bromide
and a lower valent metal compound, provided that said fluorinated alkyl
sulfonyl chloride or bromide contains more fluorine atoms than hydrogen
atoms.
2. A polymerization process, comprising, contacting, at a temperature of
about 90.degree. C. to about 200.degree. C., a free radically
polymerizable olefin with a fluorinated alkyl sulfonyl chloride or
bromide, provided that said fluorinated alkyl sulfonyl chloride or bromide
contains more fluorine atoms than hydrogen atoms.
3. The process as recited in claim 1 wherein said temperature is about
90.degree. C. to about 120.degree. C.
4. The process as recited in claim 2 wherein said temperature is about
110.degree. C. to about 150.degree. C.
5. The process as recited in claim 1 or 2 wherein said fluorinated alkyl
sulfonyl chloride or bromide has the formula C.sub.n F.sub.2n+1 SO.sub.2 X
wherein X is Cl or Br and n is 1 to 20.
6. The process as recited in claim 1 or 2 wherein in said fluorinated alkyl
sulfonyl chloride or bromide a carbon atom bound to a sulfur atom of a
sulfonyl chloride or bromide group is perfluorinated.
7. The process as recited in claim 1 wherein a metal in said lower valent
metal compound is Ru›II!, Sm›II!, Cr›II!, V›II!, Sn›II!, Fe›II!, Cu›I!, or
Ni›II!.
8. The process as recited in claim 1 wherein a metal in said lower valent
metal compound is Cu›I!.
9. The process as recited in claim 1 wherein said lower valent metal
compound is formed in situ in said process.
10. The process as recited in claim 1 wherein an oxidation state of a metal
in said lower valent metal compound is one lower than a higher oxidation
state of said metal.
11. The process as recited in claim 1 or 2 carried out in an aqueous
medium.
12. The process as recited in claim 1 or 2 wherein said fluorinated alkyl
sulfonyl chloride or bromide contain one sulfonyl chloride or sulfonyl
bromide group.
13. The process as recited in claim 1 or 2 wherein said fluorinated alkyl
sulfonyl chloride or bromide is a perfluorinated polymer.
14. The process as recited in claim 1 or 2 wherein said free radically
polymerizable olefin is a styrene or a methacrylate-type compound.
Description
FIELD OF THE INVENTION
Polymerization of free radically polymerizable olefinic monomers may be
accomplished by using a fluoroalkylsulfonyl halide and optionally a lower
valent metal compound as an initiator system. Monomers such as styrenes,
(meth)acrylics, halogenated olefins and vinyl ethers may be polymerized to
a variety of thermoplastics or elastomers.
TECHNICAL BACKGROUND
The free radical polymerization of olefinic monomers is an important
commercial process, and a wide variety of these monomers, such as
styrenes, acrylics, halogenated olefins, vinyl ethers, and others may be
homo- or copolymerized. The resultant polymers are useful as molding
resins, plastic sheet, film, and elastomers, depending upon the properties
of the particular polymer made. Many types of polymerization initiators
for these monomers are known, such as peroxides, azonitriles, various
redox couples, and others, but virtually all of these have one or more
drawbacks. Some are inherently unstable, especially to heat, and/or may
produce undesired end groups in the resulting polymers, and/or may only be
used under certain conditions such as in aqueous or non-aqueous systems,
etc. Therefore new initiation systems for these polymerizations are
constantly being sought.
M. Asscher et al., J. Chem. Soc. (1964) p. 4962-4971 report the reaction of
various aryl sulfonyl chlorides or alkyl sulfonyl chlorides and copper
chloride with various olefins such as styrene. No polymers are reported to
be products.
A. Orochov et al., J. Chem. Soc. (1969) p. 255-259 report on the reaction
of cupric chloride with an aryl sulfonyl chloride in the presence of
styrene. No polymers are reported.
N. Kamigata et al., J. Chem. Soc., Perkin Trans. I (1991) p. 627-633 report
on the reaction of perfluoroalkylsulfonyl chlorides with styrene or other
olefins in the presence of various transition metal compounds. No polymers
are reported as products.
V. Percec et al., Macromolecules, vol. 28, p. 7970-7972 (1995), and V.
Percec et al., Macromolecules, vol. 29, p. 3665-3668 (1996) describes the
polymerization of styrene in the presence of aryl sulfonyl chlorides and
certain transition metal compounds. Alkyl sulfonyl halides are not
described as being used in these papers.
SUMMARY OF THE INVENTION
This invention concerns a first polymerization process, comprising,
contacting, at a temperature of about 50.degree. C. to about 150.degree.
C., a free radically polymerizable olefin with a fluorinated alkyl
sulfonyl chloride or bromide and a lower valent metal compound, provided
that said fluorinated alkyl sulfonyl chloride or bromide contains more
fluorine atoms than hydrogen atoms.
This invention also concerns a second polymerization process, comprising,
contacting, at a temperature of about 90.degree. C. to about 200.degree.
C., a free radically polymerizable olefin with a fluorinated alkyl
sulfonyl chloride or bromide, provided that said fluorinated alkyl
sulfonyl chloride or bromide contains more fluorine atoms than hydrogen
atoms.
DETAILS OF THE INVENTION
In the processes described herein, a free radically polymerizable olefin is
present. Such olefins are well known in the art, see for instance H. Mark
et al., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed.,
Vol. 13, John Wiley & Sons, New York, 1988, p. 708-713, and include
styrenes, (meth)acrylic-type compounds, various vinyl halides such as
vinyl chloride, vinyl fluoride, vinylidene fluoride and
tetrafluoroethylene, vinyl ethers such as methyl vinyl ether and
perfluoro(methyl vinyl ether), chloroprene, isoprene, vinyl esters such as
vinyl acetate, and others. In these polymerizations, only one olefin may
be present to form a homopolymer, or more than one olefin may be present
to form a copolymer. Some combinations of monomers may not free radically
copolymerize while others will copolymerize. Such combinations are also
well known in the art. Also, copolymers of olefins which do not readily
homopolymerize under free radical conditions may be prepared using a more
readily polymerizable monomer. Examples of such monomer combinations
include tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene
and ethylene, and tetrafluoroethylene and perfluoro(alkyl vinyl ethers).
By a fluorinated alkyl sulfonyl chloride is meant a compound containing the
group --SO.sub.2 Cl, while a sulfonyl bromide contains the group
--SO.sub.2 Br (collectively these are sulfonyl halide groups herein).
Sulfonyl chlorides are preferred. Each of these compounds may contain more
than one sulfonyl chloride or sulfonyl bromide group, although one is
preferred. By fluorinated alkyl is meant that each sulfonyl halide group
is attached to an alkyl carbon atom, and the alkyl group is fluorinated
(another term for this group could be a fluorinated saturated acyclic
radical or group) and this group may in fact be an alkyl group, as in
normal --C.sub.n F.sub.2n+1 SO.sub.2 X, and alkylene group as in XO.sub.2
S(CF.sub.2).sub.8 SO.sub.2 X, a number of alkylene groups as in XO.sub.2
S›CF.sub.2 CF(CF.sub.3)O!.sub.4 CF.sub.2 CF.sub.2 SO.sub.2 X or a
trivalent group such as in FC(CF.sub.2 CF.sub.2 SO.sub.2 X).sub.3, wherein
X is chlorine or bromine. Other possibilities will be obvious to the
artisan. One or more of the sulfonyl halide groups may also be present in
a polymer, so the number of carbon atoms in the sulfonyl halide is
essentially unlimited. The alkyl group of the fluorinated alkyl group may
also be substituted. That is it may contain substituents other than
fluorine. Suitable substituents include halogen other than fluorine,
ether, aryl group(s), and the like. One or more ether groups is a
preferred substituent.
An especially preferred sulfonyl halide is normal --C.sub.n F.sub.2n+1
SO.sub.2 X wherein X is Cl or Br and n is 1 to 20. In another preferred
form of the sulfonyl halide, the carbon atom(s) attached directly to the
sulfur atom of the sulfonyl halide group(s) is (are) perfluorinated. It is
also preferred that the alkyl group of the sulfonyl halide compound be
perfluorinated.
By a lower valent metal in the first polymerization process is meant a
metal in an oxidation state from which it may change to a higher oxidation
state. Usually, such a metal is a transition metal either in the metallic
state or as a lower valent compound. Suitable lower valent metals include
Ru›II!, Sm›II!, Cr›II!, V›II!, Sn›II!, Fe›II!, Cu›I!, Ni›II!, Co›II!,
Cu›0!, Ni›0! and Fe›0!. Preferred lower valent metals are Ru›II!, Sm›II!,
Cr›II!, V›II!, Sn›II!, Fe›II!, Cu›I!, Ni›II!, and Cu›I! is more preferred.
Metal alloys containing suitable metals may also be used. When metals are
used it is unclear whether the metal itself is the active species or
whether small amounts of oxidized metal which may be present is the active
catalyst. It is preferred that in the initial lower oxidation state of the
metal, a one higher oxidation state is available to the metal, for
instance M›I!.fwdarw.M›II!, or M›II!.fwdarw.M›III!, where M is a metal.
The lower valent metal need not be added "directly". It may be formed in
situ in the process from either an even lower valent state or a higher
valent state. For instance, CuCl.sub.2 is reported to form CuCl in the
presence of styrene (M. Asscher et al., J. Chem. Soc., (1963), p. 1887),
so addition of CuCl.sub.2 to a polymerization in which styrene was present
would fulfill the requirement for the presence of a lower valent metal.
The first polymerization process is run at a temperature of about
50.degree. C. to about 150.degree. C., preferably about 90.degree. C. to
about 120.degree. C. The second polymerization process is run at a
temperature of about 90.degree. C. to about 200.degree. C., preferably
about 110.degree. C. to about 150.degree. C.
The polymerization processes described herein may be carried out in aqueous
or non-aqueous medium. By an aqueous medium is meant a liquid medium that
is at least 20 volume percent water, not including the volume of any
polymer formed. The aqueous medium may be a dispersion, emulsion, or
suspension. The sulfonyl halides described herein, especially those that
are perfluorinated, have surprisingly high stabilities in an aqueous
medium especially when that medium is neutral or acidic, see for instance
Example 12. This allows these compounds to be conveniently used in these
polymerizations in an aqueous medium.
A polymerization in a non-aqueous medium includes those in the bulk
monomer, when an organic solvent or non-solvent (for one or more
components in the polymerization) is present, or in a supercritical fluid
which is non-aqueous.
Otherwise both polymerization processes described herein may be carried out
using methods known to the artisan, see for instance H. Mark et al., Ed.,
Encyclopedia of Polymer Science and Engineering, 2nd Ed., Vol. 12, John
Wiley & Sons, New York, 1988, p. 504-555. For instance, these
polymerizations may be carried out in a batch, semi-batch or continuous
manner.
Sometimes the free radical polymerization of olefinic monomers using a
fluoroalkylsulfonyl halide and a lower valent metal compound may possess
characteristics of so-called "living" or "controlled" polymerization
processes. Such processes can lead to polymers with narrow molecular
weight distributions, as illustrated in Examples 1, 9 and 10, and may
permit formation of block copolymers by sequential addition of
polymerizable monomers. For these types of polymerizations, Cu›I! is a
preferred low valent metal, and preferred monomers are styrenes and
methacrylic-type compounds. The polymers made herein have fluoroalkyl end
groups derived from the fluorinated alkyl sulfonyl chloride or bromide.
However these end groups do not contain much, if any, sulfur from the
sulfonyl halide group. The other end of the polymer chain may have a
halide, such as chloro or bromo, end group.
In the Examples, the following abbreviations are used:
DSC--Differential Scanning Calorimetry
GPC--Gel Permeation Chromatography
Mn--number average molecular weight
Mw--weight average molecular weight
P/D--Mw/Mn
THF--tetrahydrofuran
Herein melting points measured by DSC were determined at a heating rate of
20.degree. C./min., and the melting point was taken as the peak of the
melting endotherm. GPC results are relative to a polystyrene standard.
EXPERIMENT 1
Synthesis of Perfluorobutanesulfonyl Chloride
1-Iodoperfluorobutane (934 g, 2.7 mol) was added dropwise over 1.5 hr to a
stirred, deoxygenated mixture of 800 mL of water, 375 mL acetonitrile, 236
g of sodium bicarbonate and 505 g of sodium dithionite at 28.degree. C.
This mixture was stirred at room temperature for 24 hr, warmed to
40.degree.-45.degree. C. for 1 hr, then cooled to 0.degree. C. A
precipitate was collected by filtration under nitrogen and washed with 100
mL of cold 1:1 acetonitrile:water giving 184 g of sodium
perfluorobutanesulfinate as a white powder. The filtrate was diluted with
1-L deoxygenated ethyl acetate. The organic layer was separated, washed
with 100 mL brine and evaporated to dryness to 100.degree. C. The residue
was recrystallized from isopropanol to give an additional 648 g of product
as a white solid. The total yield was 832 g (100%). A 316 g portion of
this product was dissolved in 250 mL of water and 50 mL concentrated
sulfuric acid and extracted with 3.times.100 mL of ether. The combined
ether extracts were washed with brine and concentrated under reduced
pressure. The residue was distilled through an 46 cm column giving 276.6 g
of n-perfluorobutanesulfinic acid, bp 67.degree.-73.degree. C. at 133 Pa.
.sup.19 F NMR (CDCl.sub.3) -81.6 (3F), -126.7 (2F), -122.7 (2F), -123.0
(2F).
A 92.2 g portion of the above sulfinic acid was added to 100 mL of
deoxygenated water at 8.degree.-12.degree. C. and chlorine bubbled through
the solution. A lower layer which formed was collected, dried over
anhydrous magnesium sulfate and distilled through a 46 cm column giving
62.4 g of n-perfluorobutanesulfonyl chloride, bp 105.degree. C. .sup.19 F
NMR (CDCl.sub.3) -81.2(3F), -126.3 (2F), -120.6 (2F), -104.9 (2F).
EXPERIMENT 2
Synthesis of n-Perfluorooctanesulfonyl Chloride
Sodium n-perfluorooctanesulfinate, prepared in a similar manner to the
butanesulfinate described above, (50.6 g) was slurried in 125 mL of
deoxygenated water and chlorine gas was passed into this mixture yielding
a solid mass. An additional 125 mL deoxygenated water and 125 mL of
1,1,2-trichlorotrifluoroethane were added while the chlorine addition was
continued until two distinct layers with no solid were formed. The layers
were separated and the organic layer was concentrated on a rotary
evaporator. The residue was distilled in a Kugelrohr apparatus at
80.degree. C. and 1300 Pa into a dry ice cooled receiver giving 47.7 g of
product as a white solid, mp 37.degree.-38.degree. C. .sup.19 F NMR
(CDCl.sub.3) -81.6 (3F), -126.7 (2F), -123.2 (2F), -122.2 (2F), -122.0
(2F), -121.9 (2F), -119.6 (2F), -104.8 (2F).
EXAMPLE 1
Polymerization of Styrene Using Perfluorobutanesulfonyl Chloride and
Cuprous Chloride
A clean, dry 15 mL glass polymer tube was charged with 0.10 g cuprous
chloride, 0.156 g 2,2'-bipyridine, 5.2 g (50 mmol) of purified styrene and
0.32 g (1 mmol) of n-perfluorobutanesulfonyl chloride. The resulting
mixture was subjected to 4 freeze/thaw cycles and sealed under vacuum. The
tube was shaken and then immersed in an oil bath at 120.degree. C. for 20
hr. The tube was cooled and opened and the viscous syrup was dissolved in
THF. The THF solution was passed through 5 g of silica gel to remove
metallic residues and poured slowly into 300 mL of methanol. The white
polymer was collected and dried under vacuum at 90.degree. C. giving 4.90
g of product. .sup.19 F NMR (THF) -81.2 (3F), -125.8 (2F), -124.2 (2F),
-112.2 (2F). GPC analysis (THF) Mw 10000, Mn 7260, P/D 1.38. Anal. Found:
C, 88.90; H, 7.27; Cl, 0.65, F, 3.13; S, 0.10. The presence of fluorine in
the elemental analysis and the F NMR spectrum confirm the presence of
C.sub.4 F.sub.9 end groups.
EXAMPLES 2-8
Polymerization of Styrene Using Perfluorobutanesulfonyl Chloride
The procedure of Example 1 was essentially repeated using no catalyst or
using various metallic species in place of the cuprous chloride and
bipyridine. The amount of catalyst used was one-half that of the
perfluorobutanesulfonyl chloride on a molar basis. Results are summarized
in Table 1.
TABLE 1
__________________________________________________________________________
Polymer Characterization
Example
Catalyst Yield
% F
Mn Mw P/D
__________________________________________________________________________
2 None 80% 2.26
91800
257000
2.81
3 CpRu(CH.sub.3 CN).sub.3 OSO.sub.2 CF.sub.3
46% -- 13400
27100
2.01
4 SmCl.sub.2 78% 0.52
58500
146000
2.49
5 CrCl.sub.2 68% 0.74
58400
158000
2.70
6 VCl.sub.2 72% 0.97
39000
79600
2.04
7 SnCl.sub.2 61% 1.10
3839
9200
2.40
8 FeCl.sub.2 58% 1.31
3180
5230
1.64
__________________________________________________________________________
EXAMPLE 9
Polymerization of Styrene Using Perfluorooctanesulfonyl Chloride and
Cuprous Chloride
The procedure of Example 1 was followed using 0.52 g (1 mmol) of
n-perfluoroctanesulfonyl chloride in place of the
n-perfluorobutanesulfonyl chloride. After precipitation and drying, 4.72 g
of polymer was isolated. .sup.19 F NMR (THF) -81.1 (3F), -126.3 (2F),
-123.5 (2F), -122.9 (2F), -122.0 (4F), -121.7 (2F), -112.3 (2F). GPC
analysis (THF) Mw 13300, Mn 10100, P/D 1.31. Anal. Found: C, 87.72; H,
7.09; Cl, 0.30, F, 5.70; S, 950 ppm.
EXAMPLE 10
Polymerization of Styrene Using Perfluorobutanesulfonyl Chloride and
Cuprous Chloride
The procedure of Example 1 was followed using 2.08 g (20 mmol) of styrene,
0.64 g (2 mmol) of n-perfluorobutanesulfonyl chloride, 0.20 g (2 mmol) of
cuprous chloride and 0.31 g (2 mmol) of 2,2-bipyridine. After 24 hr at
120.degree. C., the product was dissolved in THF, filtered through a short
Florisil.RTM. column, and concentrated under vacuum at 55.degree. C. to
2.47 g of white solid. .sup.19 F NMR (benzene-d.sub.6) -81.3 (3F), -126.0
(2F), -124.4 (2F), -112.5 (2F). GPC analysis (THF) Mw 3320, Mn 2570, P/D
1.29. Anal. Found: C, 80.50; H, 6.65; Cl, 2.18, F, 10.19; S, 0.29.
EXAMPLE 11
Polymerization of Methyl Methacrylate Using Perfluorooctanesulfonyl
Chloride and Cuprous Chloride
The procedure of Example 1 was followed using 0.52 g (1 mmol) of
n-perfluorooctanesulfonyl chloride, 5.01 g (50 mmol) of purified methyl
methacrylate, 0.10 g cuprous chloride and 0.47 g 2,2'-bipyridine. After
heating in a 121.degree. C. oil bath for 24 hr, the product was dissolved
in THF, passed through a Florisil.RTM. column to remove metal salts and
concentrated under vacuum to 5.27 g of white solid. GPC analysis (THF) Mw
18400, Mn 11400, P/D 1.61. Anal. Found: C, 59.28; H, 7.24; F, 3.60.
EXAMPLE 12
Preparation of an Aqueous Dispersions of Perfluorobutanesulfonyl Chloride
A solution of 2.41 g of ammonium perfluorononanoate (surfactant) in 1-L of
deionized water was processed for 5 minutes through a Microfluidizer.TM.
Model 110T with 4.14 g of n-perfluorobutanesulfonyl chloride. The mixture
was cooled by passing though a coil chilled in ice water during the
processing. A clear mixture was obtained. A .sup.19 F NMR spectrum on an
aliquot of this solution after sitting overnight at room temperature
showed peaks at -83.2 (3F), -128.0 (2F), -122.1 (2F) and -106.6 (2F) for
the perfluorobutanesulfonyl chloride in addition to peaks for the
surfactant. A second aliquot of the solution was heated in an oil bath at
100.degree. C. for 2 hr and then analyzed by .sup.19 F NMR. The spectrum
of the n-perfluorobutanesulfonyl chloride was essentially unchanged,
confirming stability of this compound in a neutral aqueous mixture. A more
concentrated mixture was prepared by adding 10.4 g of
n-perfluorobutanesulfonyl chloride to a solution of 0.5 g ammonium
perfluorononanoate in 100 mL of deionized water with processing through
the Microfluidizer.TM.. A faintly cloudy mixture was obtained which showed
the same F NMR spectrum as described above.
EXAMPLE 13
Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Using
Perfluorobutanesulfonyl Chloride in Water
A 1-L Hastelloy.RTM. C autoclave with a stainless steel agitator was
flushed with nitrogen and charged with 600 mL of deionized water and 1.45
g of ammonium perfluorononanoate. The reactor was closed, the contents
were cooled to about 10.degree. C. and the system was evacuated. Its was
pressured to 689 kPa with nitrogen and evacuated twice to remove oxygen
from the system. The reactor was then charged with 120 g of
hexafluoropropylene and 50 g of tetrafluoroethylene. The reactor contents
were heated to 100.degree. C. resulting in an internal pressure of 4.60
MPa. A 25 mL portion of the more concentrated n-perfluorobutanesulfonyl
chloride solution in water, prepared in Example 12, was injected over 5
min, resulting in a decrease in internal pressure to 3.10 MPa over the
course of 2 hr. The reactor was cooled to room temperature and vented. The
contents, a slightly cloudy dispersion with about 0.32 cm of solid on the
surface, was frozen with dry ice and allowed to thaw. The resulting
mixture was filtered on a nylon cloth. The solid was stirred with about
300 mL water while being heated to about 80.degree. C., filtered and dried
overnight in a vacuum oven at 110.degree. C. giving 50.8 g of polymer with
a DSC melting temperature of 280.6.degree. C.
EXAMPLE 14
Copolymerization of Tetrafluoroethylene and Hexafluoropropylene Using
Perfluorobutanesulfonyl Chloride in Water
The procedure of Example 13 was followed, except that the reaction mixture
was heated to 65 .degree. C. prior to injection of the
perfluorobutanesulfonyl chloride solution. The initial pressure of 2.99
MPa decreased to 2.08 MPa after injection of the initiator. Polymer (38.2
g) was isolated and had a DSC melting point of 290.8.degree. C.
EXAMPLES 15-22
Copolymerization of Tetrafluoroethylene and Hexafluoropropvlene Using
Perfluorobutanesulfonyl Chloride in Water in a Glass Reactor
A glass tube about 18 cm long and 4 cm in diameter was charged with 100 mL
of an aqueous solution containing 0.22 g of ammonium perfluorooctanoate
surfactant, 0.64 g of n-perfluorobutanesulfonyl chloride and the lower
valent metal (catalyst), if used. The tube was capped with a ground glass
stopper. A small hole, protected by a splash guard, on the side of the
tube was present to allow gas to be admitted. The glass tube was loaded
into a horizontal stainless steel pressure vessel such that the hole in
the glass tube was on the top. The pressure vessel was closed, pressured
to 689 kPa nitrogen and vented twice. It was then cooled to about
10.degree. C., evacuated and charged with 50 g of hexafluoropropylene and
25 g of tetrafluoroethylene. The tube was heated to about 108.degree. C.
and agitated for 3 hr. It was cooled and vented slowly to atmospheric
pressure. The contents of the glass tube were transferred to a plastic
bottle, using water to rinse as needed, and frozen in dry ice. After
thawing, the mixture was filtered on a nylon cloth. The solid was
suspended in about 200 mL of water and heated to about 50.degree. C. with
stirring. After cooling the solid was filtered and dried in a vacuum oven
at about 120.degree. C. The amount of polymer isolated for each experiment
is indicated in Table 2.
TABLE 2
______________________________________
Example Catalyst (g) Polymer Formed, g
______________________________________
15 None None
16 Copper wire (0.6)
13.6
17 Hastelloy .RTM. C wire (0.55)
7.4
18 Stainless steel wire (0.66)
5.9
19 CuCl (0.2) 11.5
20 NiCl.sub.2 (0.3)
7.7
21 FeCl.sub.2 (0.3)
18.5
22 FeSO.sub.4.7H.sub.2 O (0.56)
14.9
______________________________________
EXAMPLE 23
Preparation of a Perfluoropolymer with Pendant Sulfonyl Chloride Groups
A 10.5.times.64 cm piece of Nafion.TM. 115 film (lot 18466) (available from
E. I. du Pont de Nemours and Company, Wilmington, Del., U.S.A.) in the
sulfonic acid form with an equivalent weight of 1070 was immersed in 500
mL of water. Concentrated nitric acid was added and the solution was
heated to boiling for one hour to remove contaminants from the film
surface. The film was removed and washed with 4.times.1-L of deionized
water. It was immersed in 1-L of deionized water and 20 g of potassium
hydroxide pellets and stirred for 68 hr to convert the sulfonic acid
groups to the potassium sulfonate form. The film was then rinsed by
stirring with 3.times.1-L deionized water, immersed for 0.5 hr in 1-L
boiling water and dried overnight in a vacuum desiccator contained
phosphorus pentoxide.
A 1.78 g portion of the above film in three pieces was immersed in a
mixture of 40 g of phosphorus oxychloride and 40 g of phosphorus
pentachloride under nitrogen. This mixture was heated
to115.degree.-120.degree. C. and maintained for 45 hr. The film pieces
were removed, rinsed with 2.times.100 mL of carbon tetrachloride at room
temperature and 2.times.100 mL of boiling carbon tetrachloride and dried
in a vacuum oven at about 110.degree. C. Anal.: Found C, 201.8; F, 60.18;
S, 3.15; Cl, 1,51. An infrared spectrum of the treated film showed a sharp
band at 1427 cm.sup.-1, the infrared and elemental analyses confirming the
presence of sulfonyl chloride groups in the polymer.
EXAMPLE 24
Grafting of Styrene to a Polymer Containing Sulfonyl Chloride Groups
A 0.538 g portion of the polymer film made in Example 23 was immersed in a
mixture of 25 mL of toluene and 5.2 g of styrene. Argon was bubbled into
this mixture for 1 hr. 2,2'-Dipyridine (0.234 g) and cuprous chloride
(0.05 g) were added and the mixture was heated to reflux. After 20 hr the
polymer sample was removed, rinsed with toluene and extracted for 1 hr in
boiling toluene. It was then extracted in turn with 5% aqueous
hydrochloric acid at 60.degree. C., boiling concentrated hydrochloric acid
and two portions of boiling concentrated ammonium hydroxide. After rinsing
with several portions of water, the polymer sample was dried in a vacuum
oven at 105.degree. C. The product polymer was a light green, opaque and
somewhat brittle film, in contrast to the clear, colorless, flexible
starting film. It weighed 0.823 g, an increase of 0.285 g (53%). A surface
infrared spectrum of the film was essentially identical to that of an
authentic spectrum of polystyrene. The weight increase and the infrared
spectrum confirmed grafting of styrene to the original polymer film.
EXPERIMENT 3
Synthesis of n-Perfluorobutanesulfonyl Bromide
Sodium n-perfluorobutanesulfinate (213.5 g), prepared as described in
Experiment 1, was dissolved in 500 mL of deoxygenated water under nitrogen
and cooled to 5.degree. C. Bromine (50 mL) was added over 1 hr. This
mixture was allowed to warm to room temperature over 1 hr and then heated
at 35.degree.-40.degree. C. for 1 hr. It was diluted with an additional
500 mL of water and stirred for 1 hr at 35.degree.-40.degree. C. The
mixture was cooled to room temperature and a lower layer was separated.
This material was washed with aqueous sodiumthiosulfate solution and water
and dried over anhydrous magnesium sulfate giving 233 g of crude product.
This was combined with the product from a similar reaction using 28.5 g of
sodium n-perfluorobutanesulfinate and distilled through a 15 cm
fractionating column giving 192.6 g of product, bp 54.degree. C. at 8.0
kPa. .sup.19 F NMR (CDCl.sub.3) -81.1 (3F), -126.4 (2F), -120.7 (2F),
-104.4 (2F).
EXAMPLE 25
Grafting of Methyl Methacrylate to a Polymer Containing Sulfonyl Chloride
Groups
A 0.483 g portion of the polymer film made in Example 23 was immersed in
6.18 g of freshly distilled methyl methacrylate in a polymer tube. This
mixture was subjected to 4 freeze/evacuate/thaw cycles and sealed under
vacuum. The tube was immersed in an oil bath at 130.degree. C. for 16 hr.
The tube was cooled and opened and the block of opaque polymer was
extracted 4 times with 250 mL portions of methylene chloride. The
insoluble material was dried at 120.degree. C. in a vacuum oven giving
3.2186 g, a weight increase of 2.7356 g (566%). An infrared spectrum of
the product showed a strong absorption at 1730 cm.sup.-1. Anal. Found: C,
52.35; H, 6.60; F, 9.72; S, 0.73.
EXAMPLE 26
Solution Polymerization of Styrene Using Perfluorooctanesulfonyl Chloride
and Cuprous Chloride
A 100 mL round bottom flask was charged with 5.18 g (0.01 mol) of
n-perfluorooctanesulfonyl chloride, 20 mL of toluene and 5.2 g (0.05 mol)
of styrene. The solution was bubbled with argon for 1 hr. 2,2'-Bipyridine
(2.34 g, 0.015 mol) and cuprous chloride (0.5 g, 0.005 mol) were added.
This mixture was heated under argon at 110.degree. C. for 20 hr. The
product mixture was passed through a short column of Florisil.RTM.,
eluting with an additional 125 mL of toluene. The combined toluene
solutions were washed with 3.times.25 mL of 10% aqueous hydrochloric acid
and 2.times.15 mL of water and evaporated to dryness. The solid polymer
was dried at 80.degree. C. and 7 Pa giving 7.3 g of product. GPC analysis
(THF) Mw 1672, Mn 1436, P/D 1.16. Anal. Found: C, 64.33; H, 4.79; F,
27.62.
EXAMPLE 27
Solution Polymerization of Methyl Methacrylate Using
Perfluorobutanesulfonyl Bromide and Cuprous Bromide
A 50 mL round bottom flask was charged with 20 mL of toluene. The toluene
was bubbled with argon and 5.0 g (50 mmol) methyl methacrylate, 0.156 g (1
mmol) of 2,2'-bipyridine, 0.143 g (1 mmol) of cuprous bromide and 0.36 g
(1 mmol) of perfluorobutanesulfonyl bromide were added. The mixture was
heated to reflux under argon and maintained overnight. The cooled mixture
was passed through a short column of Florisil.RTM., eluting with toluene.
The combined toluene solutions were washed with 5% aqueous hydrochloric
acid and water and dried over anhydrous magnesium sulfate. The toluene
solution was concentrated to about 30 mL and poured into 400 mL of
methanol. The precipitated polymer was collected and dried at 100.degree.
C. and 13 Pa giving 1.5 g of white solid. GPC analysis (THF) Mw 12300, Mn
12606, P/D 1.13. Anal. Found: C, 59.15; H, 7.65; F, 1.94.
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